Radiation sensitive resin composition

ABSTRACT

A radiation sensitive resin composition which contains an alicyclic olefin resin obtained by ring-opening polymerization of a polymerizable monomer containing an alicyclic olefin monomer having carboxyl group using a ruthenium catalyst, followed by hydrogenation, an acid-generating agent, a crosslinking agent and a solvent; and a transparent resin pattern film formed on a substrate obtained by laminating a resin film formed by using the resin composition described above to the substrate, followed by irradiation with an active radiation to form a latent pattern and developing the pattern by bringing the resin film having the latent pattern into contact with a developing solution. The resin composition exhibits excellent property for development and storage stability. The transparent resin pattern film obtained from the resin composition exhibits excellent specific permittivity, transparency, dimensional stability under heating, solvent resistance and flatness and can be utilized as the resin film for electronic parts.

TECHNICAL FIELD

The present invention relates to a radiation sensitive resin compositionsolubility of which in a developing solution changes by irradiation withan active radiation such as particle beams and electronic beams. Moreparticularly, the present invention relates to a radiation sensitiveresin composition advantageously used as the material for forming aresin pattern film having excellent transparency which is used as aresin film for electronic parts such as the protective film, theflattening film and the electric insulation film.

BACKGROUND ART

In electronic parts such as liquid crystal display devices, integratedcircuit devices and solid image forming devices and color filters forliquid crystal displays, functional resin films for electronic partssuch as protective films for preventing degradation and damages ofdevices and displays, flattening films for flattening the surface of thedevices and wiring and electric insulation films for maintaining theelectric insulation are disposed. In liquid crystal display devices ofthe thin film transistor type and integrated circuit devices, interlayerinsulation films for insulation between wirings arranged as layers aredisposed as the functional resin films for electronic parts.

However, occasionally, an interlayer insulation film having sufficientflatness cannot be formed even when a thermosetting material heretoforeknown as the material for forming electronic parts is used, and a novelmaterial sensitive to radiation which is used for forming insulationfilms and enables fine patterns to be formed has been desired. Moreover,as the density of the wiring and the devices increases recently, thedesired material is required to have a small permittivity.

In response to the above requirement, compositions comprising analicyclic olefin resin soluble in an alkali which is obtained byring-opening polymerization of a norbornene-based monomer having anester group, followed by hydrogenation of the obtained polymer andhydrolysis of the ester group portion to form bonded carboxylic group,an acid-generating agent and a crosslinking agent, are proposed(Japanese Patent Application Laid-Open Nos. Heisei 10(1998)-307388 andHeisei 11(1999)-52574).

However, it has been confirmed by the present inventors that the resinfilms formed by using the radiation sensitive resin compositionsdescribed in the above two patent publications have poor storagestability and property for development although permittivity, waterabsorption, flatness, solvent resistance and dimensional stability underheating are excellent. Since a radiation sensitive resin composition isused in an industrial process, in general, after the composition isprepared in a suitable vessel and, then, transferred to an apparatus forapplying to a substrate or the like, the storage stability of thecomposition is very important.

As the result of intensive studies based on the above knowledge by thepresent inventors to obtain a radiation sensitive resin compositionwhich is suitable for industrial process, it was found that an alicyclicolefin resin soluble in an alkali could be obtained without thehydrolysis step when an alicyclic olefin monomer having an acidic groupsuch as carboxyl group was polymerized in the presence of a catalystcontaining ruthenium (a ruthenium catalyst) and the obtained polymer washydrogenated in place of obtaining, as specifically described inexamples of the above publications, an alicyclic olefin resin byring-opening polymerization of an alicyclic olefin monomer having analkyloxycarbonyl group in the presence of a catalyst containing tungsten(a tungsten catalyst), followed by hydrogenation of the obtained polymerand hydrolysis of the hydrogenation product to obtain carboxylic acid,and that the resin obtained by the present inventors exhibited thestorage stability suitable for the industrial process and provided aradiation sensitive resin composition exhibiting an improved propertyfor development. The present invention has been completed based on theabove knowledge.

Patent Reference 1

-   -   Japanese Patent Application Laid-Open No. Heisei 10(1998)-307388

Patent Reference 2

-   -   Japanese Patent Application Laid-Open No. Heisei 11(1999)-52574

DISCLOSURE OF THE INVENTION

In accordance with the present invention, a radiation sensitive resincomposition which comprises (A) an alicyclic olefin resin soluble in analkali, (B) an acid-generating agent, (C) a crosslinking agent and (D) asolvent is provided. In the composition, the alicyclic resin soluble inan alkali is a ring-opening polymer having an acidic group which isobtained by ring-opening polymerization of a polymerizable monomercomprising an alicyclic olefin monomer having an acidic group in thepresence of a catalyst comprising ruthenium, followed by hydrogenatingthe obtained polymer.

In accordance with the present invention, a process for forming a resinpattern film on a substrate which comprises laminating a resin filmformed by using the resin composition described above to the substrate,irradiating the resin film with an active radiation to form a latentpattern in the resin film and developing a pattern by bringing the resinfilm having the latent pattern into contact with a developing solution,is also provided.

In accordance with the present invention, a transparent resin patternfilm formed in accordance with the process described above and anelectric insulation film comprising the resin pattern film describedabove are also provided.

Specifically, the present invention provides:

(1) A radiation sensitive resin composition which comprises (A) analicyclic olefin resin soluble in an alkali, (B) an acid-generatingagent, (C) a crosslinking agent and (D) a solvent, wherein the alicyclicresin soluble in an alkali is a ring-opening polymer having an acidicgroup which is obtained by ring-opening polymerization of apolymerizable monomer comprising an alicyclic olefin monomer having anacidic group in a presence of a catalyst comprising ruthenium, followedby hydrogenating an obtained polymer;(2) A radiation sensitive resin composition described in (1), whereinthe acidic group is carboxyl group or phenolic hydroxyl group;(3) A radiation sensitive resin composition described in (1), whereinthe alicyclic olefin monomer having an acidic group is an alicyclicolefin monomer represented by following formula (1):

wherein R¹ to R⁴ each independently represent hydrogen atom or a grouprepresented by —X_(m)—R′, X representing a divalent group, mrepresenting 0 or 1, and R′ representing an alkyl group having 1 to 7carbon atoms which may have substituents, an aromatic group or an acidicgroup; at least one of R¹ to R⁴ represents a group represented by—X_(m)—R′ in which R′ represents an acidic group; and n represents aninteger of 0 to 2;(4) A radiation sensitive resin composition described in (1), whereinthe catalyst comprising ruthenium is a catalyst comprising as a maincomponent an organoruthenium compound in which a neutralelectron-donating ligand is coordinated;(5) A radiation sensitive resin composition described in (4), whereinthe neutral electron-donating ligand is a heterocyclic carbene compoundhaving nitrogen atom;(6) A radiation sensitive resin composition described in (1), whereinthe polymerizable monomer further comprises an alicyclic olefin monomerin which a group having an aromatic group and an aprotic polar group arebonded;(7) A process for forming a resin pattern film on a substrate whichcomprises laminating a resin film comprising a radiation sensitive resincomposition described in any one of (1) to (6) to the substrate,irradiating the resin film with an active radiation to form a latentpattern in the resin film and developing a pattern by bringing the resinfilm having the latent pattern into contact with a developing solution;(8) A transparent resin pattern film formed in accordance with a processdescribed in (7); and(9) A resin film for electronic parts comprising a resin pattern filmdescribed in (8).

THE MOST PREFERRED EMBODIMENT TO CARRY OUT THE INVENTION

The alicyclic olefin resin soluble in an alkali of component (A) used inthe radiation sensitive resin composition of the present invention is anring-opening polymer obtained by polymerizing an alicyclic olefinmonomer (an unsaturated aliphatic cyclic hydrocarbon) having an acidicgroup in the presence of a catalyst comprising ruthenium, followed byhydrogenating the obtained polymer. Since the ring-opening polymer hasan acidic group, the polymer is soluble in an alkaline solution. Theacidic group is a group forming a Brφnsted acid, examples of whichinclude carboxyl group and phenolic hydroxyl group (hydroxyphenylgroup).

In the present invention, one or more polymerizable monomers other thanthe alicyclic olefin monomer having an acidic group (referred to asother monomers, hereinafter) can be used.

The fraction of the alicyclic olefin monomer having an acidic group inthe entire polymerizable monomers used for obtaining the alicyclicolefin resin soluble in an alkali of component (A) is, in general, 10 to100% by mole, preferably 15 to 90% by mole, more preferably 20 to 80% bymole and most preferably 25 to 70% by mole. The fraction in this rangeis advantageous since the balance between the transparency, theresistance to discoloration under heating and the property fordevelopment is excellent.

The number of the acidic group in the alicyclic olefin monomer is notparticularly limited. It is preferable that the number of the acidicgroup is 1 or 2. When a compound having two or more acidic groups in themolecule is used as the alicyclic olefin monomer having an acidic group,the property for achieving excellent patterning can be obtained evenwhen the above fraction is relatively small within the above range(specifically, in general, 10 to 50% by mole, preferably 20 to 40% bymole and more preferably 25 to 35% by mole). In contrast, when acompound having just one acidic group in the molecule is used as thealicyclic olefin monomer having an acidic group, it is preferable thatthe above fraction is set at a relatively great value within the aboverange (specifically, in general, 50 to 90% by mole, preferably 55 to 80%by mole and more preferably 60 to 75% by mole).

The alicyclic olefin monomer having an acidic group may have othergroups showing no acidity such as aromatic groups, alcoholic hydroxylgroup and carbonyl group in combination with the acidic group.

Preferable examples of the alicyclic olefin monomer having an acidicgroup include compounds represented by the following formula (1):

(In the above formula, R¹ to R⁴ each independently represent hydrogenatom or a group represented by —X_(m)—R′, X representing a divalentgroup, m representing 0 or 1, and R′ representing an alkyl group having1 to 7 carbon atoms which may have substituents, an aromatic group or anacidic group; at least one of R¹ to R⁴ represents a groups representedby —X_(m)—R′ in which R′ represents an acidic group; and n represents aninteger of 0 to 2.)

In formula (1), R¹ to R⁴ each independently represent hydrogen atom or agroup represented by —X_(m)—R′ (X representing a divalent group, mrepresenting 0 or 1, and R′ representing an alkyl group having 1 to 7carbon atoms which may have substituents, an aromatic group or an acidicgroup); and at least one, preferably one or two, of R¹ to R⁴ representgroups represented by —X_(m)—R′ in which R′ represents an acidic group.It is more preferable that one or two of R¹ to R⁴ represent groupsrepresented by —X_(m)—R′ in which R′ represents an acidic group, and therest of R¹ to R⁴ represent hydrogen atom. When any two of R¹ to R⁴represent groups represented by —X_(m)—R′ in which R′ represents anacidic group, it is preferable that the two such groups are groupsbonded to different carbon atoms (for example, the combination of groupsrepresented by R¹ and R³).

In formula (1), X represents a divalent group. Examples of the divalentgroup include alkylene groups, arylene groups and —O—, —R—C(═O)—R— (Rrepresenting an alkylene group or an arylene group). From the standpointof the stability, alkylene groups and arylene groups are preferable.

In formula (1), m represents 0 or 1 and, preferably, 0 from thestandpoint of the productivity.

The alkyl group is a linear, branched or cyclic saturated hydrocarbongroup having 1 to 7 carbon atoms. Examples of the alkyl group includemethyl group, ethyl group, n-propyl group, isopropyl group, cyclopropylgroup, n-butyl group, isobutyl group, t-butyl group, s-butyl group,cyclobutyl group, n-pentyl group, 1-methybutyl group, 2-methylbutylgroup, isopentyl group, cyclopentyl group, n-hexyl group, 1-methypentylgroup, 2-methylpentyl group, 2-ethylbutyl group, 3-methylpentyl group,isohexyl group, cyclohexyl group, 1-methylcyclopentyl group, n-heptylgroup, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group,2-ethyl-3-methylbutyl group, isoheptyl group, cycloheptyl group and3-methylcyclohexyl group.

The above alkyl group may have a substituent such as halogen atoms,hydroxyl group (alcoholic hydroxyl group), —C(═O)—R, —OR, —C(═O)—O—R and—OC(═O)—R(R in these formulae representing an alkyl group or an arylgroup).

The other monomer which can be used as the polymerizable monomer may bean alicyclic olefin monomer (having no acidic groups) or a monomer whichis not alicyclic (unsaturated aliphatic chain hydrocarbon) such asethylene. From the standpoint of the heat resistance, the amount of themonomer which is not alicyclic is, in general, 50% by mole or less,preferably 40% by mole or less, more preferably 30% by mole and mostpreferably 20% by mole or less based on the amount of the entirepolymerizable monomers.

Preferable examples of the other monomer include alicyclic olefinmonomers having a group having an aromatic group and an aprotic polargroup, alicyclic olefin monomers having no polar groups and alicyclicolefin monomers having no aromatic groups but having an aprotic polargroup. Examples of the aromatic group include phenyl group, naphthylgroup, anthracenyl group and phenanthrene group. Phenyl group ispreferable due to the excellent sensitivity. Hydrogen atoms in thearomatic group may be substituted with other atoms such as halogen atomsor organic groups such as alkyl groups.

It is sufficient that the aprotic polar group is a monovalent ormultivalent aprotic group of atoms containing a heteroatom having anoncovalent electron pair such as oxygen atom, nitrogen atom and sulfuratom. Examples of the aprotic polar group include N,N-disubstitutedamino groups, carbonyl group, carbonyloxycarbonyl group, oxycarbonylgroup, ether group, thioether group, N-substituted amide groups andN-substituted imide groups.

Preferable examples of the group having an aromatic group and an aproticpolar group include N-phenyl substituted imide groups such asN-phenyldicarboxyimide group; N-phenyl substituted amide groups such asN-phenylamide group; and phenyl ester groups such as phenoxycarbonylgroup and methoxycarbonyloxyphenyl group. More preferable examples ofthe group having an aromatic group and an aprotic polar group includeN-phenyldicarboxyimide group.

The alicyclic olefin monomer having no polar groups may have nonpolargroups. Examples of the nonpolar group include aromatic hydrocarbongroups such as phenyl group and aliphatic hydrocarbon groups such asmethyl group, ethyl group, isopropyl group and cyclohexyl group.

Examples of the polymerizable monomer used for obtaining the alicyclicolefin resin of component (A) used in the present invention will bedescribed later.

The alicyclic olefin resin of component (A) used in the presentinvention is obtained by ring-opening polymerization of polymerizablemonomers such as the alicyclic olefin monomer having an acidic group andother monomers used where necessary in the presence of the rutheniumcatalyst, followed by hydrogenation of the obtained polymer(hydrogenation of the double bond in the main chain).

The ruthenium catalyst used in the present invention is a catalystcomprising ruthenium which accelerates the polymerization and is,preferably, a catalyst comprising as the main component anorganoruthenium compound in which a neutral electron-donating ligand iscoordinated. The neutral electron-donating ligand in the organorutheniumcompound is a ligand having the neutral charge when the ligand isseparated from the central atom, i.e., ruthenium.

In the preferable organoruthenium compound used in the presentinvention, an anionic ligand is coordinated. The anionic ligand is aligand having a negative charge when the ligand is separated fromruthenium. A counter ion may further be present in the organorutheniumcompound. The counter ion is an anion forming an ion pair with theruthenium cation and is not particularly limited as long as the anioncan from the above pair.

Typical examples of the organoruthenium compound advantageously used inthe present invention include compounds represented by the followingformula (2):[(L²)_(c)(Y²)_(d)Ru═(C═)_(e)CQ₂]_(y)  (2)(In the above formula (2), a plurality of L² each independentlyrepresent a neutral electron-donating ligand, a plurality of Y² eachindependently represent an anionic ligand, a plurality of Q eachindependently represent hydrogen atom or a hydrocarbon group having 1 to20 carbon atoms which may have halogen atoms, nitrogen atom, oxygenatom, silicon atom, phosphorus atom or sulfur atom, c, d and y eachindependently represent an integer of 1 to 4, and e represents 0 or 1.)

Examples of the neutral electron-donating ligand include oxygen atom,water, carbonyls, amines, pyridines, ethers, nitrites, esters,phosphines, phosphinites, phosphites, stibines, sulfoxides, thioethers,amides, aromatic compounds, diolefins which may be cyclic, olefins whichmay be cyclic, isocyanides, thiocyanates and heterocyclic carbenecompounds having nitrogen atom. The polymerization activity isoccasionally enhanced when, among the above ligands, a pyridine such asbipyridine; a phosphine such as triphenylphosphine andtricyclohexylphosphine; an aromatic compound such as p-cymene; a cyclicdiolefin such as cyclopentadiene; or a heterocyclic carbene compoundhaving nitrogen atom such as 1,3-dimesitylimidazolin-2-ylidene and1,3-dimesitylimidazolidin-2-ylidene; is coordinated.

Examples of the anionic ligand include halogen atoms such as F, Br, Cland I; hydrides, diketonate groups such as acetylacetonate group,cyclopentadienyl group, allyl group, alkenyl groups, alkyl groups, arylgroups, alkoxyl groups, aryloxyl groups, alkoxycarbonyl groups,arylcarboxyl groups, carboxyl group, alkyl- and arylsulfonyl groups,alkylthio groups, alkenylthio groups, arylthio groups, alkylsulfonylgroups and alkylsufinyl groups. The polymerization activity is excellentwhen, among the above ligands, a halogen atoms, cyclopentadienyl group,allyl group, an alkyl group or an aryl group is coordinated.

Examples of the atom or the group represented by Q in the above formula(2) include hydrogen atom, alkenyl groups, alkynyl groups, alkyl groups,alkylidene groups, aryl groups, carboxyl group, alkoxyl groups,alkenyloxyl groups, alkynyloxyl groups, aryloxyl groups, alkoxycarbonylgroups, alkylthio groups, alkenylthio groups, arylthio groups,alkylsulfonyl groups and alkylsulfinyl groups. The polymerizationactivity is occasionally enhanced when, among the above atom or thegroups, an alkyl group, an alkylidene group, an aryl group, an alkoxylgroup, an aryloxyl group, an alkylthio group or an arylthio group having1 to 100 carbon atoms is coordinated.

Examples of the polymerization catalyst represented by formula (2)include bis(tricyclohexylphosphine)benzylideneruthenium dichloride,bis(triphenylphosphine)-3,3-diphenylpropenylideneruthenium dichloride,bis(tricyclohexylphosphine)phenylvinylideneruthenium dichloride,bis(tricyclohexylphosphine)-t-butylvinylideneruthenium dichloride,bis(1,3-diisopropylimidazolin-2-ylidene)benzylideneruthenium dichloride,bis(1,3-dicyclohexylimidazolin-2-ylidene)benzylidenerutheniumdichloride, (1,3-dimesitylimidazolin-2-ylidne)(tricyclohexylphosphine)benzylideneruthenium dichloride and(1,3-dimesitylimidazolidin-2-ylidene)-(tricyclohexylphosphine)benzylidenerutheniumdichloride.

For enhancing the polymerization activity of the above polymerizationcatalyst, a neutral electron-donating compound may be added in an amountby weight 1 to 100 times as much as the amount by weight of theruthenium metal. Examples of the neutral electron-donating compoundinclude pyridines, phosphines and heterocyclic carbene compounds havingnitrogen atom described above such as1,3-diisopropoylimidazolin-2-ylidene and1,3-dimesitylimidazolidin-2-ylidene.

When the polymerization catalyst represented by formula (2) is used, forexample, a diazo compound such as N₂CHCOOEt, an acetylene compound suchas phenylacetylene or a silyl compound such as Et₂SiH and Ph₂MeSiH maybe added in an amount by weight 1 to 100 times as much as the amount byweight of ruthenium metal to enhance the polymerization activity. In theabove, Et means ethyl group, Ph means phenyl group, and Me means methylgroup.

The ring-opening polymerization may be conducted in a solvent or withoutusing solvents. It is preferable that the polymerization is conducted ina solvent since the hydrogenation can be conducted without isolating thepolymer after the polymerization. The solvent used for thepolymerization is not particularly limited as long as the polymerizablemonomer is dissolved and the polymerization is not adversely affected.Examples of the solvent include aliphatic hydrocarbons such as pentane,hexane and heptane; alicyclic hydrocarbons such as cyclopentane,cyclohexane, methylcyclohexane, dimethylcyclohexane,trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane,decahydronaphthalene, bicycloheptane, tricyclodecane,hexahydroindenecyclohexane and cyclooctane; aromatic hydrocarbons suchas benzene, toluene, xylene and misitylene; hydrocarbons having nitrogenatom such as nitromethane, nitrobenzene, acetonitrile, propionitrile andbenzonitrile; ethers such as diethyl ether, tetrahydrofuran and dioxane;and hydrocarbons having halogen atoms such as chloroform,dichloromethane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene andtrichlorobenzene. Among these solvents, solvents having a specificpermittivity in the range of 2 to 5 and preferably in the range of 2.1to 4.5 and mixed solvents prepared by mixing two or more solvents in amanner such that the specific permittivity is within the above range arepreferable. The specific permittivity of a solvent is disclosed in“Organic Solvent”, the second edition, John A. Riddick and Emory E.Toops, Jr., 1955.

When the polymerization is conducted in a solvent, it is preferable thatthe concentration of the polymerizable monomer is 1 to 50% by weight,more preferably 2 to 45% by weight and most preferably 5 to 40% byweight. When the concentration of the polymerizable monomer is smallerthan 1% by weight, productivity of the polymer is occasionally poor.When the concentration exceeds 50% by weight, viscosity after thecopolymerization is excessively great, and the hydrogenation after thepolymerization is occasionally slow.

The amount of the polymerization catalyst expressed as the ratio of theamount by mole of the ruthenium metal to the amount by mole of thealicyclic olefin monomer in the polymerization catalyst (rutheniummetal:monomer) is 1:100 to 1:2,000,000, preferably 1:500 to 1:1,000,000and more preferably 1:1,000 to 1:500,000. When the amount of thecatalyst exceeds the amount expressed by 1:100, removal of the catalystoccasionally becomes difficult. When the amount of the catalyst is lessthan the amount expressed by 1:2,000,000, the sufficientcopolymerization activity is not obtained, occasionally. The temperatureof the polymerization is not particularly limited. The temperature ofthe polymerization is, in general, −100 to 200° C., preferably −50 to180° C., more preferably −30 to 160° C. and most preferably 0 to 140° C.The time of the polymerization is, in general, 1 minute to 100 hours.The time of the polymerization can be adjusted in accordance with theprogress of the polymerization.

The hydrogenation is the reaction to convert the unsaturated doublebonds in the main chain of the ring-opening polymer into saturatedsingle bonds, in general, by introducing hydrogen in the presence of ahydrogenation catalyst.

As the hydrogenation catalyst used for the hydrogenation, a catalystconventionally used for hydrogenation of olefin compounds can be used.

Examples of the hydrogenation catalyst include Ziegler catalysts whichare combinations of transition metals and alkali metal compounds such ascombinations of cobalt acetate and triethylaluminum, nickelacetylacetonate and triisobutylaluminum, titanocene dichloride andn-butyllithium, zirconocene dichloride and sec-butyllithium andtetrabutoxy titanate and dimethylmagnesium; homogeneous catalystsincluding noble metal complex catalysts such as organorutheniumcompounds represented by the above general formula (2),chlorotris-(triphenylphosphine)rhodium and ruthenium compounds describedin Japanese Patent Application Laid-Open Nos. Heisei 7 (1995)-2929,Heisei 7 (1995)-149823, Heisei 11 (1999)-209460, Heisei 11(199)-158256and Heisei 11 (1999)-193323 and heterogeneous catalysts containing ametal such as nickel, palladium, platinum, rhodium and rutheniumsupported on a support such as carbon, silica, diatomaceous earth,alumina and titanium oxide. Specific examples of the hydrogenationcatalyst include nickel/silica, nickel/diatomaceous earth,nickel/alumina, palladium/carbon, palladium/silica,palladium/diatomaceous earth, palladium/alumina, ruthenium/silica,ruthenium/alumina, ruthenium/carbon, platinum/silica, platinum/alumina,rhodium/alumina and rhodium/carbon.

Since the carbon-carbon double bond can be hydrogenated selectivelywithout side reactions such as modification of functional groups, thenoble metal complex catalysts having a noble metal such as rhodium andruthenium are preferable, and ruthenium catalysts in which compoundsexhibiting a great electron-donating property such as heterocycliccarbene compounds having nitrogen atom and phosphines are coordinatedare more preferable, among the above hydrogenation catalysts.

Since the ruthenium catalyst works also as the polymerization catalystas described above, the hydrogenation can be conducted successivelyafter the ring-opening polymerization. In this case, the activity of theruthenium catalyst can be enhanced by adding a catalyst modifier.Examples of the catalyst modifier include vinyl compounds such as ethylvinyl ether and α-olefins.

The hydrogenation is, in general, conducted in an organic solvent. Theorganic solvent can be suitably selected in accordance with thesolubility of the formed hydrogenation product. The same solvent as thatused in the polymerization described above may be used. Therefore, afterthe polymerization has been completed, the hydrogenation can beconducted by adding the hydrogenation catalyst to the reaction mixturewithout replacing the solvent with another solvent.

The preferable condition for the hydrogenation is different depending onthe used hydrogenation catalyst. It is preferable that the condition isselected in a range such that unsaturated bonds other than the C═Cdouble bond formed from the alicyclic olefin monomer are nothydrogenated. From this standpoint, the temperature of the reaction is,in general, −20 to 250° C., preferably −10 to 220° C. and morepreferably 0 to 200° C. The pressure of hydrogen is, in general, 0.01 to10 MPa, preferably 0.05 to 8 MPa and more preferably 0.1 to 5 MPa. Whenthe temperature of the reaction is lower than −20° C., the rate of thereaction is small. When the temperature of the reaction exceeds 250° C.,side reactions tend to take place. When the pressure of hydrogen issmaller than 0.01 MPa, the rate of hydrogenation is small. When thepressure of hydrogen exceeds 10 MPa, a reaction apparatus resistant to ahigh pressure is necessary. The time of the hydrogenation is suitablyselected to control the degree of hydrogenation. When the time of thehydrogenation is in the range of 0.1 to 50 hours, 50% or more,preferably 70% or more, more preferably 80% or more and most preferably90% or more of the carbon-carbon double bonds in the main chain of thecopolymer can be hydrogenated.

The weight-average molecular weight of the alicyclic olefin resin ofcomponent (A) is, in general, 500 to 20,000, preferably 1,000 to 15,000and more preferably 2,000 to 10,000.

Examples of the polymerizable monomer used as the material for thealicyclic olefin resin of component (A) are shown in the following.

Examples of the alicyclic olefin monomer which is the polymerizablemonomer having an acidic group used in the present invention include thecompounds represented by formula (1) shown above.

Examples of the compound represented by formula (1) include8-hydroxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,5-hydroxycarbonylbicyclo[2.2.1]hept-2-ene,5,6-dihydroxycarbonylbicyclo-[2.2.1]hept-2-ene,5-methyl-5-hydroxycarbonylbicyclo[2.2.1]hept-2-ene,5-carboxymethyl-5-hydroxycarbonylbicyclo[2.2.1]hept-2-ene,8,9-di-hydroxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-methyl-8-hydroxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-methyl-8,9-dihydroxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-carboxy-methyl-8-hydroxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,11-hydroxycarbonylhexacyclo[6.6.1.1^(3,6).1^(10,13).0^(2,7).0^(9,14)]heptadeca-4-ene,11,12-dihydroxycarbonylhexacyclo[6.6.1.1^(3,6).1^(10,13).0^(2,7).0^(9,14)]heptadeca-4-ene,11-methyl-11-hydroxycarbonylhexacyclo[6.6.1.1^(3,6).1^(10,13).0^(2,7).0^(9,14)]-heptadeca-4-eneand11-carboxymethyl-11-hydroxycarbonylhexacyclo-[6.6.1.1^(3,6).1^(10,13).0^(2,7).0^(9,14)]heptadeca-4-ene.

Examples of the other monomer include the following compounds.

Examples of the alicyclic olefin monomer having a group having anaromatic group and an aprotic polar group include monomers in which anaprotic polar group is directly bonded to a group having an aromaticring such as N-(4-phenyl)-(5-norbornene-2,3-dicarboxyimide),N-(4-phenyl)(5-norbornene-2,3-dicarboxyimide),2-(4-methoxyphenyl)-5-norbornene, 2-(4-methoxyphenyl)-5-norbornene and2-benzyloxycarbonyl-5-norbornene.

Examples of the monomer providing a monomer unit derived from analicyclic olefin monomer having no polar groups includebicyclo[2.2.1]-hept-2-ene [also known as (a.k.a.) norbornene],5-ethylbicyclo[2.2.1]hept-2-ene, 5-butylbicyclo[2.2.1]hept-2-ene,5-ethylidenebicyclo[2.2.1]hept-2-ene,5-methylidenebicyclo[2.2.1]hept-2-ene, 5-vinylbicyclo[2.2.1]hept-2-ene,tricyclo[4.3.0.1^(2,5)]deca-3,7-diene (a.k.a. dicyclopentadiene),tetracyclo-[7.4.0.1^(10,13).0^(2,7)]trideca-2,4,6,11-tetraene (a.k.a.1,4-methano-1,4,4a,9a-tetrahydrofluorene),tetracyclo[8.4.0.1^(11,14).0^(2,8)]tetradeca-3,5,7,12-11-tetraene,tetracyclo[4.4.0.1^(2,5).1^(7,10)]deca-3-ene (a.k.a.tetracyclododecene),8-methyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-ethyltetracyclo-[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-methylidenetetracyclo[4.4.0.1^(2,5).1^(7,10)]-dodeca-3-ene,8-ethylidenetetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-vinyl-tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-propenyltetracyclo-[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,pentacyclo-[6.5.1.1^(3,6).0^(2,7).0^(9,13)]pentadeca-3,10-diene,pentacyclo[7.4.0.1^(3,6).1^(10,13).0^(2,7)]pentadeca-4,11-diene,cyclobutene, cyclopentene, cyclohexene, 3,4-dimthylcyclopentene,3-methylcyclohexene, 2-(2-methylbutyl)-1-cyclohexene, cyclooctene,3a,5,6,7a-tetrahydro-4,7-methano-1H-indene, cycloheptene,vinyl-cyclohexene, vinylcyclohexane, cyclopentadiene, cyclohexadiene,5-phenylbicyclo[2.2.1]hept-2-ene,1,4-methano-1,4,4a,5,10,10a-hexahydro-anthracene,5-phenylbicyclo[2.2.1]hept-2-ene,tetracyclo[6.6.0.1^(2,5).1^(8,13)]-tetradeca-3,10,12tetraene and8-phenyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene.

As the alicyclic olefin monomer having no aromatic groups but having anaprotic polar group,8-methyl-8-methoxycarbonyltetracyclo-[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,bicyclo[2.2.1]hept-2-ene-5,6-dicarboxylic acid anhydride,tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene-8,9-dicarboxylic acidanhydride,hexacyclo[6.6.1.1^(3,6).1^(10,13).0^(2,7).0^(9,14)]heptadeca-4-ene-11,12-dicarboxylicacid anhydride, 5-methoxycarbonylbicyclo[2.2.1]hept-2-ene,5-cyanobicyclo[2.2.1]hept-2-ene and5-methyl-5-methoxycarbonyl-bicyclo[2.2.1]hept-2-ene can be used.

As the monomer which is not alicyclic, unsaturated hydrocarbons can beused. Examples of the unsaturated hydrocarbons include ethylene andα-olefins having 2 to 20 carbon atoms such as ethylene, propylene,1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene,3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene,4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene,3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,1-hexadecene, 1-octadecene and 1-eicosene; and non-conjugated dienessuch as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadieneand 1,7-octadiene. It is known that, among the above compounds, theα-olefin compounds such as 1-hexene and 1-octene and the diene compoundswork also as the molecular weight modifier in the ring-openingpolymerization when these compounds are added in an amount of 0.1 to 10%by mole based on the amount of the entire monomers.

The acid-generating agent of component (B) used in the present inventionis a compound generating an acid by irradiation with an activeradiation.

Examples of the acid-generating agent providing a pattern of thepositive-type include quinonediazidesulfonic acid esters. Thequinonediazidesulfonic acid ester is an ester compound which is widelyused as the photosensitive agent and obtained from aquinonediazidesulfonic acid halide such as1,2-naphthoquinonediazide-5-sulfonic acid chloride and a phenol havingat least one phenolic hydroxyl group. Examples of the phenol include2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone,2-bis(4-hydroxyphenyl)propane, tris(4-hydroxyphenyl)methane,1,1,1-tris(4-hydroxy-3-methylphenyl)ethane,1,1,2,2-tetrakis(4-hydroxyphenyl)ethane,1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane, oligomers ofnovolak resins and oligomers obtained by copolymerization of phenols anddicyclopentadiene (Japanese Patent No. 3090991).

The amount of the acid-generating agent is, in general, 0.5 to 100 partsby weight, preferably 1 to 50 parts by weight and more preferably 10 to30 parts by weight per 100 parts by weight of the alicyclic olefinresin. When the amount of the acid-generating agent is excessivelysmall, there is the possibility that the fraction of the residual filmand the resolution become poor. When the amount of the acid-generatingagent is excessively great, there is the possibility that heatresistance and transmission of light become poor.

In the present invention, the crosslinking agent of component (C) is acompound forming a crosslinked structure between molecules of thecrosslinking agent by heating or a compound forming a crosslinkedstructure between molecules of the alicyclic olefins resin by reactionwith the alicyclic olefin resin. Specifically, the crosslinking agentsis a compound having two or more reactive groups. As the reactive group,amino group, carboxyl group, hydroxyl group, epoxy group, isocyanategroup and vinyl group are preferable.

Examples of the crosslinking agent include aliphatic polyamines such ashexamethylenediamine; aromatic polyamines such as 4,4′-diaminodiphenylether and diaminodiphenyl sulfone; azide compounds such as2,6-bis(4′-azidobenzal)cyclohexanone and 4,4′-diazidodiphenyl sulfone;polyamides such as nylon, polyhexamethylenediamine terephthalamide andpolyhexamethylene isophthalamide; melamines such asN,N,N′,N′,N″,N″-(hexaalkoxy methyl)melamines; glycol urylsN,N′,N′,N′″-(tetraalkoxymethyl)glycol uryls; acrylate compounds such asethylene glycol di(meth)acrylate and epoxyacrylate resins;isocyanate-based compounds such as hexamethylene diisocyanate-basedpolyisocyanates, isophorone diisocyanate-based polyisocyanates, andtolylene diisocyanate-based polyisocyanates; hydrogenateddiphenylmethane diisocyanate-based polyisocyanates;1,4-di(hydroxymethyl)cyclohexane; 1,4-di(hydroxymethyl)norbornane;1,3,4-trihydroxycyclohexane; and epoxy compounds and resins having analicyclic structure.

The amount of the crosslinking agent is not particularly limited and canbe decided as desired taking the degree of heat resistance required forthe pattern into consideration. The amount of the crosslinking agent is,in general, 1 to 100 parts by weight, preferably 5 to 80 parts byweight, more preferably 10 to 70 parts by weight and most preferably 20to 50 parts by weight per 100 parts by weight of the alicyclic olefinresin. The heat resistance tends to decrease when the amount is lessthan the above range or exceeds the above range.

In the present invention, a solvent dissolving the components describedabove can be used as the solvent of component (D). Examples of thesolvent include alcohols such as methanol, ethanol, propanol, butanoland 3-methoxy-3-methylbutanol; cyclic ethers such as tetrahydrofuran anddioxane; cellosolve esters such as methylcellosolve acetate andethylcellosolve acetate; glycol ethers such as ethylene glycol monoethylether, ethylene glycol monopropyl ether, ethylene glycol mono-t-butylether, propylene glycol monoethyl ether, propylene glycol monopropylether, propylene glycol monobutyl ether, diethylene glycol monomethylether, diethylene glycol monoethyl ether and dipropylene glycolmonomethyl ether; propylene glycol alkyl ether acetates such aspropylene glycol propyl ether acetate; aromatic hydrocarbons such asbenzene, toluene and xylene; ketones such as methyl ethyl ketone,cyclohexanone, 2-heptanone and 4-hydroxy-4-methyl-2-pentanone; esterssuch as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate,ethyl ethoxyacetate, ethyl hydroxyacetate, methyl2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl3-methoxypropionate, ethyl 3-ethoxy-propionate, methyl3-ethoxypropionate, ethyl acetate, butyl acetate and ethyl lactate; andaprotic polar solvents such as N-methylformamide, N,N-dimethylformamide,N-methyl-2-pyrrolidone, N-methylacetamide, N,N-dimethylacetamide,dimethyl sulfoxide and γ-butyrolactone.

To prevent formation of striation (traces formed by coating) and improvethe property for development, the radiation sensitive resin compositionof the present invention may further comprise various types ofsurfactants. Examples of the surfactant include nonionic surfactantssuch as polyoxyethylene lauryl ether and polyoxyethylene dilaurate;fluorine-based surfactants such as surfactants of the EFTOP seriesmanufactured by SHIN AKITA KASEI Co., Ltd., surfactants of the MEGAFACKseries manufactured by DAINIPPON INK AND CHEMICALS INCORPORATED,surfactants of the FLUORAD series manufactured by SUMITOMO 3M LIMITED.and surfactants of the ASAHI GUARD series manufactured by ASAHI GLASSCo., Ltd.; silane-based surfactants of the organosiloxane polymer KPseries manufactured by SHIN-ETSU CHEMICAL Co., Ltd.; and acrylic acidcopolymer-based surfactants of the POLYFLOW series manufactured byKYOEISHA CHEMICAL Co., Ltd. The surfactant is used, where necessary, inan amount, in general, 2 parts by weight or less and preferably 1 partby weight or less based on 100 parts by weight of the solid componentsin the radiation sensitive resin composition.

The radiation sensitive resin composition of the present invention mayfurther comprise functional silane coupling agents such asγ-glycidoxypropyltrimethoxysilane as the auxiliary adhesive to improveadhesion with the substrate. The amount of the auxiliary adhesive is, ingeneral, 20 parts by weight or less, preferably 0.05 to 10 parts byweight and more preferably 1 to 10 parts by weight per 100 parts byweight of the alicyclic olefin resin.

The radiation sensitive resin composition of the present invention mayfurther comprise antistatic agents, storage stabilizers, defoamingagents, pigments, dyes, antioxidants and sensitizers, where necessary.

The components described above may each be used singly or as acombination of two or more.

The radiation sensitive resin composition of the present invention is asolution obtained by mixing the above components in accordance with aconventional process. The concentration of solid components in theradiation sensitive resin composition of the present invention can beset at a desired value taking the required thickness of the resin filminto consideration. In general, the concentration is 5 to 40% by weightfrom the standpoint of the operability.

It is preferable that the prepared radiation sensitive resin compositionis used after foreign substances are removed with a filter of about 0.1to 5 μm.

The radiation sensitive resin composition of the present invention canbe advantageously used as the material for various resin pattern filmfor electronic parts, examples of which include protective films fordevices such as display devices and integrated circuit devices and colorfilters for liquid crystal displays, flattening films for flattening thesurface of devices and wiring, insulation films for maintaining electricinsulation (including interlayer insulation films and solder resistfilms which are the electric insulation films in liquid crystal displaydevices of the thin transistor type and integrated circuit devices).

A resin pattern film is formed on a substrate by laminating the resinfilm comprising the radiation sensitive resin composition of the presentinvention described above to the substrate, irradiating the resin filmwith an active radiation through a mask pattern to form a latent patternin the resin film and developing a resin pattern by bringing the resinfilm having the latent pattern into contact with a developing solution.

The process for laminating the resin film to the substrate is notparticularly limited. For example, the surface of a substrate is coatedwith the radiation sensitive resin composition of the present invention,and the formed coating layer is dried to form a resin film having nofluidity on the substrate.

As the process for coating the surface of a substrate or a support withthe radiation sensitive resin composition of the present invention,various processes such as the spray coating process, the roll coatingprocess and rotation coating process can be used. The formed coatinglayer is dried by heating, and a resin film having no fluidity can beobtained. When the resin film is formed directly on the surface of thesubstrate, the condition of heating is, in general, at 60 to 120° C. forabout 10 to 600 seconds although the condition is different depending onthe types and the relative amounts of the components. In the process inwhich the coating film is formed directly on the substrate by coatingthe surface of the substrate with the radiation sensitive resincomposition, followed by drying the formed coating layer, the heatingfor the drying is called, in general, the “prebaking”.

The obtained resin film is irradiated with an active radiation, and alatent pattern is formed in the resin film. The type of the activeradiation is not particularly limited. Examples of the active radiationinclude visible light, ultraviolet light, far ultraviolet light, X-ray,electron beams and proton beams. Among these radiations, visible lightand ultraviolet light are preferable. The amount of radiation applied bythe irradiation can be set as desired in accordance with the type andthe thickness of the resin film. The pattern may be formed byirradiation through a mask having the pattern or by directly drawing thepattern with electron beams.

The developing solution is an aqueous solution obtained by dissolving analkaline compound into water. Examples of the alkaline compound includeinorganic alkalis such as sodium hydroxide, potassium hydroxide, sodiumcarbonate, sodium silicate, sodium metasilicate and ammonia water;primary amines such as ethylamine and n-propylamine; secondary aminessuch as diethylamine and di-n-propylamine; tertiary amines such astriethylamine, methyldiethylamine and N-methylpyrrolidone; alcoholamines such as dimethylethanolamine and triethanolamine; quaternaryammonium salts such as tetramethylammonium hydroxide, tetraethylammoniumhydroxide, tetrabutylammonium hydroxide and choline; and cyclic aminessuch as pyrrol, piperidine, 1,8-diazabicyclo[5.4.0]undeca-7-ene and1.5-diazabicyclo-[4.3.0]nona-5-ene. The alkaline compound may be usedsingly or as a mixture of two or more.

The time of the development is not particularly limited. The time of thedevelopment is, in general, 30 to 180 seconds. The process for bringingthe developing solution into contact with the resin film having a latentpattern is not particularly limited. For example, the paddle process,the spray process or the dipping process can be used.

The temperature of the development is not particularly limited. Thetemperature of the development is, in general, 15 to 35° C. andpreferably 20 to 30° C.

After the desired resin pattern film is formed on the substrate asdescribed above, where necessary, the substrate may be brought intocontact with a rinsing liquid in accordance with a conventional processto remove unnecessary residues of development remaining on thesubstrate, the back face of the substrate and end portions of thesubstrate. After the substrate has been brought into contact with therinsing liquid, in general, the substrate is dried with the compressedair or a compressed nitrogen gas to remove the rinsing liquid. Wherenecessary, the entire surface of the substrate having the resin patternlayer may be irradiated with the active radiation.

The resin pattern film formed on the substrate is, where necessary,cured by heating (the “post baking”). From the standpoint of theimprovement in the heat resistance of the resin pattern film, it ispreferable that the resin pattern film is heated. The process for theheating is not particularly limited. For example, the heating isconducted using a heating apparatus such as a hot plate and an oven. Thetemperature of the heating is not particularly limited. The temperatureof the heating is, in general, 150 to 300° C. and preferably 200 to 250°C. The time of the heating is not particularly limited. For example, thetime of the heating is, in general, 5 to 60 minutes when a hot plate isused and 30 to 90 minutes when an oven is used.

The resin pattern film formed by using the radiation sensitive resincomposition of the present invention is a transparent resin filmexhibiting excellent transparency. The resin pattern film of the presentinvention can be advantageously used as the resin film for variouselectronic parts, examples of which include electronic devices such assemiconductor devices, light emitting diodes and various types ofmemories, coating materials for hybrid IC, MCM and printed circuitboards, interlayer insulation films of multi-layer circuit boards andinsulation films for liquid crystal displays.

EXAMPLES

The present invention will be described more specifically with referenceto Synthesis Examples and Examples in the following. The part and thepercent in the examples show the part by weight and the percent byweight, respectively, unless otherwise mentioned.

Synthesis Example 1

Into a pressure resistant glass reactor which had been purged withnitrogen gas, 100 parts by weight of8-hydroxycarbonyltetracyclo-[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene, 1.3parts by weight of 1-hexene, 0.05 parts by weight of1,3-dimesitylimidazolidin-2-ylidene)(tricyclohexylphosphine)benzylidenerutheniumdichloride and 400 parts by weight of tetrahydrofuran were placed. Theresultant mixture was stirred for 2 hours under heating at 70° C., and areaction solution was obtained. It was confirmed in accordance with thegas chromatography that the monomers did not remain in the reactionsolution. The obtained reaction solution was poured into a great amountof n-hexane, and the solid component was separated. The obtained solidcomponent was washed with n-hexane and dried at 100° C. for 18 hoursunder a reduced pressure, and a ring-opening metathesis copolymer wasobtained as a white solid. Into an autoclave equipped with a stirrer,100 parts by weight of the ring-opening metathesis copolymer, 400 partsby weight of tetrahydrofuran and 5 parts by weight of palladium/carbon(10% palladium) as the hydrogenation catalyst were placed, andhydrogenation was conducted under a hydrogen pressure of 1.0 MPa at 60°C. for 8 hours. After the reaction mixture was filtered, the reactionproduct was coagulated in a great amount of n-hexane and dried in amanner similar to that conducted above, and Polymer A which was analicyclic olefin resin having carboxyl group was obtained. It wasconfirmed from the ¹H-NMR spectrum that the degree of hydrogenation ofthe polymer was 100%, and the entire amount of carboxyl group wasremaining. The degree of hydrogenation is the value based on the amountof the aliphatic C═C bond formed from the alicyclic olefin monomer bythe ring-opening polymerization.

Synthesis Example 2

In accordance with the same procedures as those conducted in SynthesisExample 1 except that 100 parts by weight of a mixture of8-hydroxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene andbicyclo-[2.2.1]hept-2-ene (80/20 as the ratio of the amounts by mole)was used in place of8-hydroxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene, PolymerB which was an alicyclic olefin resin having carboxyl group wasobtained. It was confirmed from the ¹H-NMR spectrum that the degree ofhydrogenation of the polymer was 100%, and the entire amount of carboxylgroup was remaining.

Synthesis Example 3

In accordance with the same procedures as those conducted in SynthesisExample 1 except that 100 parts by weight of a mixture of8-hydroxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene and8-methyl-8-methoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene(95/5 as the ratio of the amounts by mole) was used in place of8-hydroxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene, PolymerC which was an alicyclic olefin resin having an acidic group wasobtained. It was confirmed from the ¹H-NMR spectrum that the degree ofhydrogenation of the polymer was 100%, and the entire amount of carboxylgroup was remaining.

Synthesis Example 4

In accordance with the same procedures as those conducted in SynthesisExample 1 except that 100 parts by weight of a mixture of8-hydroxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-methyl-8-methoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-eneand bicyclo[2.2.1]-hept-2-ene (78/2/20 as the ratio of the amounts bymole) was used in place of8-hydroxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene, PolymerD which was an alicyclic olefin resin having an acidic group wasobtained. It was confirmed from the ¹H-NMR spectrum that the degree ofhydrogenation of the polymer was 100%, and the entire amounts ofcarboxyl group and ester group were remaining.

Comparative Synthesis Example 1

In accordance with the polymerization process using a tungsten catalystwhich was disclosed in Synthesis Example 1 of Japanese PatentApplication Laid-Open No. Heisei 10 (1998)-307388, the ring-openingpolymerization of8-methyl-8-methoxycarbonyltetracyclo-[4.4.0.1²⁵.1^(7,10)]-dodeca-3-enewas conducted, and a ring-opening polymer having a weight-averagemolecular weight of 16,800 was obtained. The conversion of thepolymerization was about 100%. After the obtained ring-opening polymerwas hydrogenated, the product of the hydrogenation was hydrolyzed at190° C. for 4.5 hours, and an alicyclic olefin resin having a polargroup (Polymer E) was obtained. The degree of hydrogenation was 100%,and the degree of hydrolysis was 95%.

Comparative Synthesis Example 2

In accordance with the same procedures as those conducted in SynthesisExample 1 except that 100 parts by weight of a mixture of8-methyl-8-methoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-eneand 5-methyl-5-methoxycarbonylbicyclo[2.2.1]hept-2-ene (80/20 as theratio of the amounts by mole) was used in place of8-hydroxycarbonyltetracyclo-[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene, thering-opening polymerization and the hydrogenation were conducted. Then,the hydrolysis was conducted in accordance with the same procedure asthat conducted in Comparative Synthesis Example 1, and an alicyclicolefin resin having a polar group (Polymer F) was obtained. The degreeof hydrogenation was 100%, and the degree of hydrolysis was 97%.

The mole fractions of carboxyl group and methyloxycarbonyl group in theobtained polymers are shown in Table 1.

TABLE 1 Methyloxycarbonyl Polymer Carboxyl group group A 100%  0% B 80%0% C 95% 5% D 78% 2% E 95% 5% F 78% 2%

Example 1

The alicyclic olefin resin obtained in Synthesis Example 1 (Polymer A)in an amount of 100 parts by weight, 550 parts by weight ofcyclohexanone as the solvent, 20 parts by weight of a condensate of1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenyl propane (1 mole) and1,2-naphthoquinonediazide-5-sulfonic acid chloride (1.9 moles) as theacid-generating agent, 25 parts by weight of CYMEL 300 as thecrosslinking agent, 5 parts by weight ofγ-glycidoxypropyltrimethoxysilane as the auxiliary adhesive and 0.05parts by weight of MEGAFACK F172 (manufactured by DAINIPPON INK ANDCHEMICALS INCORPORATED) as the surfactant were mixed, and a solution wasprepared. The prepared solution was filtered through a Millipore filterhaving a pore size of 0.45 μm, and a solution of a radiation sensitiveresin composition was prepared. The prepared solution was applied to asilicon substrate, a glass substrate and a substrate having a siliconoxide film with a step of 1 μm (this substrate will be referred to as astepped substrate) in accordance with the spin coating process. Thecoated substrates were prebaked on a hot plate at 90° C. for 2 minutes,and coating films having a thickness of 3.0 μm were formed. Masks havingprescribed patterns were placed on the silicon substrate, the glasssubstrate and the stepped substrate, and ultraviolet light having awavelength of 365 nm and an intensity of 5 mW/cm² was applied for 40seconds under the atmosphere of the air. Then, the development wasconducted at 25° C. for 60 seconds using a 0.3% aqueous solution oftetramethylammonium. Then, rinsing with ultra-pure water was conductedfor 1 minute, and thin films having patterns of the positive type wereformed. Then, the entire faces were irradiated with ultraviolet lighthaving a wavelength of 365 nm and an intensity of 5 mW/cm² for 60seconds. The silicon substrate, the glass substrate and the substratehaving a silicon oxide film with a step of 1 μm on which the patternswere formed, were heated on a hot plate at 200° C. for 30 minutes forpost baking of the pattern film and the coating film, and a siliconsubstrate, a glass substrate and a stepped substrate on which thinpattern films were formed were obtained.

Examples 2 to 4

In accordance with the same procedures as those conducted in Example 1except that Polymer B to D were used in place of Polymer A, a siliconsubstrate, a glass substrate and a stepped substrate having thin patternfilms were obtained.

Comparative Examples 1 and 2

In accordance with the same procedures as those conducted in Example 1except that Polymer E (Comparative Example 1) and F (Comparative Example2) were used in place of Polymer A, a silicon substrate, a glasssubstrate and a stepped substrate having thin pattern films wereobtained.

The silicon substrates obtained in Examples and Comparative Exampleseach had a specific permittivity (ε) smaller than 2.85 as measured at 10kHz (at the room temperature) in accordance with the method of JapaneseIndustrial Standard C6481. After the substrates were heated in an ovenat 220° C. for 60 minutes, the substrates each had a thickness which was95% or greater of the thickness before being heated. Thus, it wasconfirmed that the silicon substrates having the thin pattern filmexhibited excellent specific permittivity and dimensional stabilityunder heating. The glass substrates obtained in Examples and ComparativeExamples each had a minimum transmittance of light (t) of 90% or greateras measured at a wavelength of 400 to 800 nm using a spectrophotometerfor ultraviolet, visible and near infrared light (V-570) manufactured byJASCO CORPORATION; a difference between the minimum transmittance oflight (t′) and the minimum transmittance of light (t) smaller than 5%,wherein the minimum transmittance of light (t′) was measured after beingheated in an oven at 220° C. for 60 minutes in accordance with the samemethod as that described above and the minimum transmittance of light(t) was measured before being heated; and a change in the thickness (S)after being dipped into dimethyl sulfoxide at 70° C. for 30 minutessmaller than 10%. Thus, it was confirmed that the transparency, theresistance to discoloration under heating and the solvent resistance ofthe coated glass substrates were excellent. Using the stepped substrateshaving the thin pattern film was formed, the size of the step wasmeasured by a thickness meter of the contact type, and the size of thestep was smaller than 0.1 μm in all cases. Thus, it was confirmed thatthe flatness was excellent.

In addition to the above evaluations, the property for development andthe storage stability of the resin (Polymers A to F) used in Examplesand Comparative Examples were evaluated in accordance with the followingmethods. The results are shown in Table 2.

(1) Property for Development

With respect to a resist pattern of the positive type formed on asilicon substrate, the scum after the development and the degree ofincomplete development were evaluated by observation by a scanningelectron microscope. When no scum after the development or incompletedevelopment was found, the result is expressed as “good”. When the scumafter the development was found although no incomplete development wasfound, the result is expressed as “scum formed”. When the incompletedevelopment was found although no scum after the development was found,the result is expressed as “incomplete development found”. When the scumafter the development and the incomplete development were found, theresult is expressed as “poor”.

(2) Storage Stability

The radiation sensitive resin compositions prepared in Examples wereeach placed into a glass ampoule and tightly sealed. After the ampouleswere left standing at the room temperature for 1 week, the solutionswere examined by visual observation. When no change was found, theresult is expressed as “good”. When the viscosity increased slightly andthe solution was slightly turbid, the result is expressed as “fair”.When the content turned into white gel, the result is expressed as“poor”.

TABLE 2 Property for development Storage stability Example 1 good goodExample 2 good good Example 3 good good Example 4 good good Comparativescum formed poor Example 1 Comparative poor poor Example 2

It is shown from the above results that the compounds obtained bypolymerization of the polymerizable monomers containing the alicyclicolefin monomer having carboxyl group in the presence of the rutheniumcatalyst, followed by hydrogenation of the obtained polymers surelyprovided the excellent property for development and storage stabilitywhile the excellent balance between the specific permittivity, thetransparency, the dimensional stability under heating, the solventresistance and the flatness was maintained (Examples 1 to 4). Incontrast, it is shown that the property for development and the storagestability were poor when the alicyclic olefin resin obtained byring-opening polymerization of the alicyclic olefin monomer having analkyloxycarbonyl group in the presence of the tungsten catalyst,followed by hydrogenation of the obtained polymer and hydrolysis of theobtained polymer to convert into carboxyl group as described in JapanesePatent Application Laid-Open No. Heisei 10(1988)307388 was used(Comparative Example 1). It is also shown that the property fordevelopment and the storage stability deteriorated when the acidic groupwas formed by hydrolysis even when the resin was obtained by thering-opening polymerization and the hydrogenation in the presence of theruthenium catalyst (Comparative Example 2).

INDUSTRIAL APPLICABILITY

In accordance with the present invention, the radiation sensitive resincomposition which exhibits not only the excellent specific permittivity,transparency, dimensional stability under heating, solvent resistanceand flatness but also the excellent property for development and storagestability can be obtained. Since the resin film obtained using thecomposition exhibits excellent transparency, the transparent resinpattern film which exhibits excellent transparency and used as the resinfilm for electronic parts such as the electronic part for liquid crystaldisplay devices, integrated circuit devices and solid image formingdevices, the color filter for liquid crystal displays, the protectivefilm, the flattening film and the electric insulation film, can beprovided.

1. A radiation sensitive resin composition which is capable of forming apositive pattern resin film which comprises (A) an alicyclic olefinresin soluble in an alkali, (B) an acid-generating agent, (C) acrosslinking agent and (D) a solvent, wherein the alicyclic resinsoluble in an alkali is a ring-opening polymer having an acidic groupwhich is obtained by ring-opening polymerization of a polymerizablemonomer comprising an alicyclic olefin monomer having an acidic group ina presence of a catalyst comprising ruthenium, followed by hydrogenatingan obtained polymer, wherein the catalyst comprising ruthenium is acatalyst comprising as a main component an organoruthenium compound inwhich a neutral electron-donating ligand is coordinated, wherein saidcrosslinking agent is a compound capable of forming a crosslinkedstructure between molecules of the crosslinking agent by heating,wherein the acidic group is a carboxyl group, and wherein the alicyclicolefin monomer having an acidic group is an alicyclic olefin monomerselected from the group consisting of8-hydroxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,5-hydroxycarbonylbicyclo[2.2.1]hept-2-ene,5,6-dihydroxycarbonylbicyclo-[2.2.1]hept-2-ene,5-methyl-5-hydroxycarbonylbicyclo[2.2.1]hept-2-ene,5-carboxymethyl-5-hydroxycarbonylbicyclo2.2.1]hept-2-ene,8,9-di-hydroxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-methyl-8-hydroxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-methyl-8,9-dihydroxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-carboxy-methyl-8-hydroxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,11-hydroxycarbonylhexacyclo[6.6.1.1^(3,6).1^(10,13).0^(2,7).0^(9,14)]heptadeca-4-ene,11,12-dihydroxycarbonylhexacyclo[6.6.1.1^(3,6).1^(10,13).0^(2,7).0^(9,14)]heptadeca-4-ene,11-methyl-11-hydroxycarbonylhexacyclo heptadeca-4-ene and11-carboxymethyl-11-hydroxycarbonylhexacyclo-[6.6.1.1^(3,6).1^(10,13).0^(2,7).0^(9,14)]heptadeca-4-ene.2. A radiation sensitive resin composition according to claim 1, whereinthe neutral electron-donating ligand is a heterocyclic carbene compoundhaving nitrogen atom.
 3. A radiation sensitive resin compositionaccording to claim 1, wherein the polymerizable monomer furthercomprises an alicyclic olefin monomer in which a group having anaromatic group and an aprotic polar group are bonded.
 4. A radiationsensitive resin composition according to claim 1, wherein theacid-generating agent is capable of providing a positive pattern.
 5. Aradiation sensitive resin composition according to claim 4, wherein theacid-generating agent capable of providing a positive pattern is aquinonediazidesulfonic acid ester obtained from a quinonediazidesulfonicacid halide and a phenol having at least one phenolic hydroxyl group. 6.A radiation sensitive resin composition according to claim 5, whereinthe quinonediazidesulfonic acid halide is1,2-naphthoquinone-diazide-5-sulfonic acid chloride.
 7. A radiationsensitive resin composition according to claim 6, wherein the phenol isselected from the group consisting of 2,3,4-trihydroxy-benzophenone,2,3,4,4′-tetrahydroxybenzophenone, 2-bis(4-hydroxy-phenyl)propane,tris(4-hydroxyphenyl)methane,1,1,1-tris(4-hydroxy-3-methylphenyl)ethane,1,1,2,2-tetrakis(4-hydroxyphenyl)ethane,1,1,3-tris-(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane, an oligomerof novolak resins and an oligomer obtained by copolymerization ofphenols and dicyclopentadiene.
 8. A radiation sensitive resincomposition according to claim 1, wherein (C) the crosslinking agent isa compound capable of forming a crosslinked structure between moleculesof the crosslinking agent by heating which is selected from the groupconsisting of an aliphatic polyamine which is hexamethylenediamine; anaromatic polyamine selected from the group consisting of4,4′-diaminodiphenyl ether and diaminodiphenyl sulfone; an azidecompound selected from the group consisting of2,6-bis(4′-azidobenzal)cyclohexanone and 4,4′-diazidodiphenyl sulfone; apolyamide selected from the group consisting of nylon,polyhexamethylenediamine terephthalamide and polyhexamethyleneisophthalamide; a melamine selected from N,N,N′,N′,N″,N″-(hexaalkoxymethyl)melamines; a glycol uryl selected fromN,N′,N″,N′″-(tetraalkoxymethyl)glycol uryls; an acrylate compoundselected from the group consisting of ethylene glycol di(meth)acrylateand an epoxyacrylate resin; an isocyanate compound selected from thegroup consisting of a hexamethylene diisocyanate polyisocyanate, anisophorone diisocyanate polyisocyanate, a tolylene diisocyanatepolyisocyanate; a hydrogenated diphenylmethane diisocyanatepolyisocyanate; 1,4-di(hydroxymethyl)cyclohexane;1,4-di(hydroxymethyl)norbornane; 1,3,4trihydroxycyclohexane; and anepoxy compound and a resin having an alicyclic structure.
 9. A processfor forming a positive pattern resin film on a substrate which compriseslaminating a resin film comprising a radiation sensitive resincomposition which comprises (A) an alicyclic olefin resin soluble in analkali, (B) an acid-generating agent, (C) a crosslinking agent and (D) asolvent, wherein the alicyclic resin soluble in an alkali is aring-opening polymer having an acidic group which is obtained byring-opening polymerization of a polymerizable monomer comprising analicyclic olefin monomer having an acidic group in a presence of acatalyst comprising ruthenium, followed by hydrogenating an obtainedpolymer to the substrate, irradiating said resin film with an activeradiation to form a latent positive pattern in the resin film anddeveloping the pattern by bringing the resin film having the latentpattern into contact with a developing solution to obtain a developedpattern, and post-baking by heating to cure the obtained pattern,wherein the catalyst comprising ruthenium is a catalyst comprising as amain component an organoruthenium compound in which a neutralelectron-donating ligand is coordinated, wherein said crosslinking agentis a compound capable of forming a crosslinked structure betweenmolecules of the crosslinking agent by heating, and wherein the acidicgroup is a carboxyl group.
 10. A process according to claim 9, whereinthe alicyclic olefin monomer having an acidic group is an alicyclicolefin monomer represented by following formula (1):

wherein R¹ to R⁴ each independently represent hydrogen atom or a grouprepresented by —X_(m)—R′, X representing a divalent group, mrepresenting 0 or 1, and R′ representing an alkyl group having 1 to 7carbon atoms which may have substituents, an aromatic group or an acidicgroup; at least one of R¹ to R⁴ represents a group represented by—X_(m)—R′ in which R′ represents a carboxyl group; and n represents aninteger of 0 to
 2. 11. A process according to claim 9, wherein theneutral electron-donating ligand is a heterocyclic carbene compoundhaving nitrogen atom.
 12. A process according to claim 9, wherein thepolymerizable monomer further comprises an alicyclic olefin monomer inwhich a group having an aromatic group and an aprotic polar group arebonded.
 13. A process for forming a resin pattern film according toclaim 9, wherein the acid-generating agent is capable of providing apositive pattern.
 14. A process for forming a resin pattern filmaccording to claim 13, wherein the acid-generating agent capable ofproviding a positive pattern is a quinonediazidesulfonic acid esterobtained from a quinonediazidesulfonic acid halide and a phenol havingat least one phenolic hydroxyl group.
 15. A process for forming a resinpattern film according to claim 14, wherein the quinonediazidesulfonicacid halide is 1,2-naphthoquinone-diazide-5-sulfonic acid chloride. 16.A process for forming a resin pattern film according to claim 15,wherein the phenol is selected from the group consisting of2,3,4-trihydroxy-benzophenone, 2,3,4,4′-tetrahydroxybenzophenone,2-bis(4-hydroxy-phenyl)propane, tris(4-hydroxyphenyl)methane,1,1,1-tris(4-hydroxy-3-methylphenyl)ethane,1,1,2,2-tetrakis(4-hydroxyphenyl)ethane,1,1,3-tris-(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane, an oligomerof novolak resins and an oligomer obtained by copolymerization ofphenols and dicyclopentadiene.
 17. A resin film of a positive patternwhich is made of a radiation sensitive resin composition which comprises(A) an alicyclic olefin resin soluble in an alkali, (B) anacid-generating agent, (C) a crosslinking agent and (D) a solvent,wherein the alicyclic resin soluble in an alkali is a ring-openingpolymer having an acidic group which is obtained by ring-openingpolymerization of a polymerizable monomer comprising an alicyclic olefinmonomer having an acidic group in a presence of a catalyst comprisingruthenium, followed by hydrogenating an obtained polymer, wherein thecatalyst comprising ruthenium is a catalyst comprising as a maincomponent an organoruthenium compound in which a neutralelectron-donating ligand is coordinated, wherein said crosslinking agentis a compound capable of forming a crosslinked structure betweenmolecules of the crosslinking agent by heating, and wherein said resinfilm formed of said resin composition is cured by heating (post baking)after the positive pattern of the resin film is developed, wherein theacidic group is a carboxyl group, and wherein the alicyclic olefinmonomer having an acidic group is an alicyclic olefin monomer selectedfrom the group consisting of8-hydroxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,5-hydroxycarbonylbicyclo[2.2.1]hept-2-ene,5,6-dihydroxycarbonylbicyclo-[2.2.1]hept-2-ene,5methyl-5-hydroxycarbonylbicyclo[2.2.1]hept-2-ene,5-carboxymethyl-5-hydroxycarbonylbicyclo[2.2.1]hept-2-ene,8,9-di-hydroxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-methyl-8-hydroxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-methyl-8,9-dihydroxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-carboxy-methyl-8-hydroxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,11-hydroxycarbonylhexacyclo[6.6.1.1^(3,6).1^(10,13).0^(2,7).0^(9,14)heptadeca-4-ene,11,12-dihydroxycarbonylhexacyclo[6.6.1.1^(3,6).1^(10,13).0^(2,7).0^(9,14)]heptadeca-4-ene,11-methyl-11-hydroxycarbonylhexacyclo[6.6.1.1^(3,6).1^(10,13).0^(2,7).0^(9,14)]-heptadeca-4-eneand11carboxymethyl-11-hydroxycarbonylhexacyclo-[6.6.1.1^(3,6).1^(10,13).0^(2,7).09,14]heptadeca-4-ene.